Process for dyeing

ABSTRACT

A process for dyeing wherein textile material is dyed or printed with a solution containing at least one fiber-reactive dyestuff in a solvent.

- United States Patent [19'] Litzler et al.

[451 Sept. 24, 1974 PROCESS FOR DYEING [75] Inventors: Alfred Litzler,Itingen; Hans Wilhelm Liechti, Oberwill; I Jean-Frederic Guye-Vuilleme,Aigle; Eugen Johann Koller, Oberwil; Branimir Milicevic, Riehen;Hans-Joerg Angliker, Basel, all of Switzerland [73] Assignee: Ciba-GeigyAG, Basle, Switzerland [22] Filed: Jan. 4, 1972 21 Appl. No.: 215,403

Related US. Application Data [63] Continuation of Ser. No. 808,661,March 19, 1969,

abandoned.

[30] Foreign Application Priority Data Jan. 27, 1969 Switzerland 1200/69Mar. 28, 1968 Switzerland 4626/68 [52] US. Cl. 8/173, 8/174 [51] Int. ClD06p 1/38 [58] Field of Search 8/93, 172, 173, 163,54, 8/174 [56]References Cited UNITED STATES PATENTS 3,097,043 Mills 8/163 OTHERPUBLICATIONS W. AS. White, Amer. Dyestuff Reporter, 7-31-1967, pp.P591-P597.

Primary Examiner-Thomas J. Herbert, J r. Attorney, Agent, or FirmJosephG. Kolodny; Edward McC. Roberts; Prabodh I. Almaula [57] ABSTRACT Aprocess for dyeing wherein textile material is dyed or printed with asolution containing at least one fiberreactive dyestuff in a solvent.

10 Claims, No Drawings PROCESS FOR DYEING This is a continuation ofapplication Ser. No. 808,661, filed Mar. 19, 1969, now abandoned.

It has been proposed to dye fibres containing amide groups, especiallynylon fibres, with fibre-reactive disperse dyestuffs in anaqueousmedium, but this procedure has not become established in practicebecause in general the dyeing has to be carried out in two steps and thedegree of colour fastness obtained is not particularly good.

This invention is based on the surprising observation that thesedisadvantages can be overcome when the dyeing is carried out in organicsolvents.

Accordingly, this invention provides a process for dyeing textilematerial made from hydrophobic staple fibres or filaments containingpolar groups, especially staple fibres or filaments containing nitrogenatoms or ester groups, wherein the textile material is dyed or printedbatchwise or, preferably, continuously, with a solution containing atleast one fibre-reactive dyestuff in a solvent or mixture of solventsthat remains to a large extent inert towards the textile material, evenat the temperature at which dyeing is carried out.

The term fibre-reactive dyestuff used in this specification has theconventional meaning and refers to a dyestuff that combines, forexample, with acylatable groups present in the fibre to form a covalentchemical bond.

The dyeing process described herein is suitable for all natural andsynthetic fibres containing nitrogen atoms and/or ester groups.Nitrogenous fibres are, for example, wool, synthetic polyamides,especially poly(hexamethyleneadipic acid amide) or nylon 66,poly(wcaprolactam) or nylon 6, poly(hexamethylene-sebacic acid amide) ornylon 610, and poly( 1 l-aminoundecanoic acid) or nylon 11, acrylic oracrylonitrile fibres, polyacrylonitrile fibres and copolymers ofacrylonitrile and other vinyl compounds, for example, acrylic esters,acrylamides, vinylpyridine, vinyl chloride or vinylidene chloride,copolymers of dicyanoethylene and vinyl acetate, and also fibres madefrom acrylonitrile block copolymers, polyurethane fibres and basicallymodified polypropylene fibres.

Examples of fibres containing ester groups are secondary acetate andtriacetate fibres and fibres made from aromatic polyesters, for example,fibres made from terephthalic acid and ethylene glycol or1,4-dimethylolcyclohexane, and copolymers of terephthalic andisophthalic acid and ethylene glycol.

When the nitrogenous fibres contain free amino groups they are capableof forming chemical bonds with the reactive dyestuffs used in accordancewith the invention. When they do not contain reactive amino groups, thedyestuff is dispersed within the fibre as in the customary dyeingprocesses for disperse dyestuffs.

The dyestuffs to be used in accordance with the invention are preferablythose of the well-known class of water-soluble or preferablywater-insoluble fibrereactive disperse dyestuffs, for example, monoazo,disazo and polyazo dyestuffs, anthraquinone, perinone, quinophthalone,oxazine, nitroso, nitro, phthalocyanine, stilbene and methine dyestuffs,including styryl, azamethine, polymethine and azostyryl dyestuffs, andalso metal-complex dyestuffs of the azo and formazan types.

Other types of suitable fibre-reactive dyestuff may also be used.

The dyestuffs to be used in accordance with the invention, which arepreferably sparingly soluble or insoluble in water, contain in themolecule at least one fibrereactive group, for example s-triazinylresidues containing one or two chlorine or bromine atoms attached to thetriazine ring, pyrimidyl residues containing one or two chlorine atomsor one or two arylsulphonyl or alkanesulphonyl groups attached to thepyrimidine ring, monoor bis(y-halogeno-B-hydroxypropyl) amino groups,B-halogeno-ethylsulphamyl residues, Bhalogeno-ethoxy groups,B-halogeno-ethylmercapto groups, 'y-halogeno-,Bhydroxypropy1sulphamy]residues, chloroacetylamino groups, vinylsulphonyl groups,2,3-epoxypr0pyl groups, or other fibre-reactive residues which arepreferably free from groups imparting solubility in water.

Suitable dyestuffs of the fibre-reactive disperse dyestuff series areindicated, for example, in British Pat. Nos. 822,500, 825,377, 833,396,838,338, 821,963, 822,948, 856,899, 848,236, 840,903, 850,977, 862,269,833,832, 836,671, 868,471, 856,898, 868,468, 855,715, 856,899, 879,263,869,100, 877,250, 870,948, 895,424, 877,591, 901,434, 880,886, 917,873,1,090,005 and 984,841, and also in US. Pat. No. 3,122,533 and FrenchPat. No. 1,276,443.

The following are given as examples of dyestuffs that can be used inaccordance with the invention:2-hydroxy-5-methyl-4-(4",6"-dichloro-s-triazinyl-2- amino)azobenzene,2-chloro-4-ethanesulphonyl-4'-[N-B-hydroxyethyl-N- B-( 4 ,6-dichloro-s-triazinyl-2-amino ethylamino]azobenzene,

4-(4' ,6 -dichloro-s-triazinyl-2-amino)-2- methylazobenzene,2-hydroxy-5-methyl-4-(4' ,6 dibromo-s-triazinyl-2-amino) azobenzene,2-hydroxy-5-methyl-4-(4"-chloro-6"-B-hydroxyethylamino-s-traizinyl-2-amino )azobenzene, 2-hydroxy-5-methyl-44 '-chloro6 -anilino-striazinyl-2-amino)-azobenzene,

2-hydroxy-5 -rnethyl-4 4 -chloro-6 -amino-striazinyl-2- amino)azobene,2-chloro-4-ethanesulphonyl-4-[N-B-hydroxyethyl-N- B-( 4 '-chloro-6'hydroxy-striazinylamino)ethylamino]azobenzene,

2-hydroxy-5 -methyl-4 4 '-bromo-6' N,N-di( B- hydroxyethyl)aminos-triazinyl-2-amino]azobenzene,2-hydroxy-5-methyl-4-(4"-chloro-6"phenyl-striazinyl-2-amino) azobenzene,

4-amino-4 4 'chloro-6' '-phenyl-s-triazinyl-2- amino)azobenzene,

l-[4-(4 ,6 '-dichloro-s-triazinyl-2-amino )ani1ino]- anthraquinone,

1- 4 chloro-6 -phenoxy-s-triazinyl-2-amino)anilino anthraquinone,4-(4",6"-dichloro-s-triazinyl-2-amino)-2,4- dinitrodiphenylamine,

4 4' -chloro-6' -methoxy-s-triazinyl-2amino )2,4- dinitrodiphenylamine,

2-hydroxy-s-methyl-4 '-(4 ,6 -dichloropyrimidinyl-2- amin0)-azobenzene,

1 ,4-bis('y-chloro-B-hydroxypropy1)aminoanthraquinone,4-B-chloroethylsulphonylphenylazo-4-B-hydroxyethylaminonaphthalene,

3 4 4-B-chloroethylsulphonyl-2-methyl-5-N-ethyl-N-B- alcohols, forexample, methanol, ethanol, n-propanol hydroxyethylaminoazobenzene, andisopropanol, ketones, for example, acetone, ethers2-chloro-4-Bchloroethylsulphonyl-2'-methyl-5-di(B- and acetals, forexample, dioxan, tetrahydrofuran, hydroxyethyl) aminoazobenzene, Iglycerolformaldehyde and glycolformaldehyde, andl-methylamino-4-B-chloroethylaminoanthraquinone, 5 also acetonitrile andpyridine, diacetone alcohol andl,4'-(4",6"-dichloro-s-triazinyl-2-amino)phenylazo-Z- higher-boilingglycol derivatives, for example, ethylene naphthol, glycol monomethylether, ethylene glycol monoethyl1-amino-2-B-bromoethoxy-4-hydroxyanthraquinone, ether, ethylene glycolmonobutyl ether and diethylene1-amino-4-hydroxy-2,B-(B-chloroethoxy)ethoxyanglycol monomethyl ether,diethylene glycol monoethyl thraquinone, l ether, thiodiglycol,polyethylene glycols, provided they1-amino-2,,8-(B-bromoethoxyanthraquinone, are liquid at roomtemperature, ethylene carbonate,2-cyano-4-methylsulphonyl-2'-'y-chlorocrotonylaminoy-butyrolactone andespecially the group of active sol-4'-bis(B-hydroxyethyl)aminoazobenzene, vents miscible with water whichboil at a temperature l,B-hydroxyethylamino-4B-(B',B'- above 120 C, forexample, N,N-dimethylformamide,dibromoacryl)aminoethylamino-S,8-dihydroxyanl5 N,N-dimethylacetamide,bis-(dimethylamido)- thraquinone, methane phosphate,tris-(dimethylarnido)-phosphate, and also the dyestuffs of the followingformulae obtain- N-methylpyrrolidone, l,5-dimethylpyrrolidone, able inaccordance with British Pat. No. 984,841: N,N-dimethylmethoxyacetamide,N,N,N,N-

tetramethylurea, tetramethylenesulphone (sulpholan), 3-methylsulpholanand dimethylsulphoxide.

ll T There are three preferred sub-groups in the series of hydrophilicsolvents, namely 1) those suitable for disoH2-NH-co-oH o1 solving linearsynthetic polymers or polycondensates capable of being spun, forexample, acrylonitrile poly- Y mers, (2) those miscible with water inall proportions,

0 NH-C Hr and (3) solvents free from hydroxyl groups.

NH Specially preferred are mixtures of chlorinated aliz phatichydrocarbons and up to 50 percent of a hydro- H @A CH3 1 philic solvent,especially an amide of a low-molecular OH NH CO CH 01 weight fatty acid,for example, dimethylacetamide or dimethylformamide.

I The process of the invention is preferably carried out NH-Q-CHEwithout the addition of dispersing agents with the advantage that thedyed textile material is more easily and A specially preferred use forthe process in accordance cleaned. The addition of surfactants to thedyeing or with the invention is the dyeing of filament fabrics. paddingliquor is optional.

Suitable solvents which have [0 be substantially inert Importantsurfactants are particularly those of the towards the staple fibres Ol'filaments at the temfollowing classes of non-ionic mpound; perature,that is to say, must not dissolve the staple a, ethers f l h d nd f xle, fibres filaments, for example, hydrophobic polyoxalkylated fattyalcohols, polyoxalkylated polyvents which are immiscible or onlyslightly miscible 1 l xalk l t d m rea mn and aliphatic amines, withwater, for example, eyclohexanol, benzyl alcohol, l lk l ik l andalkyinaphthols, esters, for example, ethyl acetate, propyl acetate,butyl l lk l d alkylarylmemaptans and l l acetate, ethers, for example,diisopropylether or dimines p y oxide, ketones, for p y t ylb. fattyacid esters of ethylene glycols and polyethyl ketone, acetophenone 0rcyclohexanone, yd a ene glycols, fatty acid esters of propylene glycoland bons, for example, benzene, xylene or toluene and habutylene glycol,fatty acid esters of glycerol or polyglylogenated hydrocarbons, forexample, Carbon te acerols and of pentaerythritol, and also of sugaralcochloride, chloroform, methylene chloride, tl'lClllOfOfithhols, forexample, sorbitol, sorbitans and saccharose. ylene, perchloroethylene,trichloroethane, tetrachloroc. N-hydroxyalkyl-carboxylic acid amides,polyoxalkethane, dibromoethylene or chlorobenzene. ylated carboxylicacid amides and sulphonamides.

Hydrophilic solvents miscible with water are a spe- It is advantageousto use, for example, surfactants of cially preferred class of solvents,for example, aliphatic the following groups: the addition productsobtained from 8 mols of ethylene oxide and 1 mol of para-tert.-octylphenol; from or 6 mols of ethylene oxide and castor oil; from molsof ethylene oxide and the alcohol C H OH; also the addition products ofethylene oxide with di-[a-phenylethyll-phenols, polyethyleneoxide-tert.-dodecylthioethers or polyaminepolyglycol ethers, or theaddition products obtained from 15 or 30 mols of ethylene oxide and 1mol of the amine C H NH or C H ,NH

In the batchwise exhaustion method of dyeing, the textile material to bedyed may be in the form of loose material, a web, yarn, a knitted fabricor a woven fabric. Dyeing may be carried out in various types ofapparatus, for example, pack-dyeing machines, cheesedyeing machines,jigs, winch becks, and so forth, depending on the nature of the materialto be dyed.

The dyeing plant may be open to the ambient atmosphere (for example, viaa reflux condenser) or it may be of the closed, for example,pressurized, type, and dyeing may be carried out under atmosphericpressure or superatmospheric pressure.

When the material has been dyed to the required depth of shade, it isremoved from the dyebath and the solvent still adhering to it is removedeither by a steam or hot-air treatment.

The dyeing process is however preferably carried out in a continuousmanner, the textile material dyed in this way being mainly woven fabricsand carpets of all kinds; some kinds of knitted material can also bedyed continuously. The material is impregnated or printed, especiallypadded, and is then subjected to a heat treatment to fix the dyestuff onthe fibre, preferably by a dry heat treatment at a temperature below thesoftening point of the fibre.

Impregnation on apadding mangle may be carried out either at roomtemperature or at an elevated temperature. After the passage through thedyestuff solution, the material is squeezed as required to a liquoruptake of about 50 to 130 percent referred to the dry weight of thematerial.

On leaving the padding mangle or printing machine, the impregnated orprinted material may be dried if necessary; for example, it may be driedin a stream of air heated, for example to to 90 C, the treatment beingof short duration, or it may be freed of most of the dyestuff solutionstill adhering to it by other means, for example, by centrifuging, or itmay be subjected to fixation or thermofixation as it is. Fixation iscarried out at a temperature above 100 C, preferably at a temperature ofat least 170 to 240 C. On no account should the fixation temperature beas high as the softening temperature of the fibre.

Thermofixation may be carried out, for example, by steaming in saturatedor unsaturated steam, or preferably by a dry heat treatment, forexample, contact heat, a treatment with high-frequency alternatingcurrent, or infra-red radiation.

The optimum fixation conditions without damage to the fibre can bedetermined by a simple preliminary trial.

Fixation can also be carried out by a so-called coldbatching process inwhich the padded and squeezed fabric is batched up at room temperaturewithout intermediate drying, wrapped in a plastic cover if necessary,and then left for some time, for example, for 24 hours, at roomtemperature. The fabric is finally unwrapped and freed from solvent bydrying.

The following Examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

EXAMPLE 1 A nylon 66 filament fabric (anorak fabric) is padded cold witha solution of 10 parts of the dyestuff of the formula in 1,000 parts ofdimethylacetamide, squeezed to a liquor uptake of 30 percent referred tothe dry weight of the fabric, dried at 40 to 50 C in a stream of warmair and then thermofixed for one minute at 200 C in a thermofixationunit (dry air). A level, brilliant yellow dyeing is obtained in which alarge proportion of dyestuff is chemically bound.

EXAMPLE 2 Padding is carried out in the manner described in Example 1,but using a mixture of 900 parts of perchloroethylene and 100 parts ofdimethylacetamide as solvent. The fabric is then squeezed to a liquoruptake of 42 percent referred to the dry weight of the material. Abrilliant yellow dyeing is obtained.

EXAMPLE 3 The same brilliant and level dyeing as that described inExample 2 is obtained by padding in the manner described in that Exampleand then fixing the dyestuff by steaming for 3 minutes at 100 C in apad-steam unit. The proportion of chemically bound dyestuff in thedyeing is smaller than that present in the dyeing obtained by theprocess described in Example 2.

Example 4 EXAMPLE 5 A nylon 66 fabric is padded cold with a solution of10 parts of the dyestuff of the formula N N CIH al lNagmg in 1,000 partsof a mixture comprising percent of perchloroethylcne and 10 percent ofdimethylacetamide, squeezed to a liquor uptake of 42 percent referred tothe dry weight of the material, dried at 40 to 50 C in a stream of warmair and then thermofixed for 1 minute at 200 C. A level, brilliantyellow dyeing is obtained in which a large proportion of dyestuff ischemically bound.

EXAMPLE 6 The procedure described in Example 5 is followed,

but using 20 parts of the dyestuff of the formula .A level, orangedyeing containing a high proportion of chemically bound dyestuff isobtained.

EXAMPLE 7 The procedure described in Example 5 is followed,

but using 20 parts of the dyestuff of the formula dissolved indimethylacetamide without the addition of solvent and the fabric issqueezed to a liquor uptake of 30 percent. A level, orange dyeingcontaining a high proportion of chemically bound dyestuff is obtained.

I EXAMPLE 8 Dyeing is carried out in the manner described in Example 7,but using mixture of 90 percent of perchloroethylene and 10 percent ofdimethylacetamide as solvent. The padded fabric is squeezed to a liquoruptake of 42 percent. A level, orange dyeing containing a highproportion of chemically bound dyestuff is obtained.

EXAMPLE 9 Dyeing is carried out in the manner described in Example 8,but using the dyestuff of the formula l zHs obtained by acylation withchloroacetyl chloride. A level, red dyeing containing a larger portionof chemically bound dyestuff is obtained.

EXAMPLE l0 Dyeing is carried out in the manner described in Example 9,but using as substratum a polyester fabric (Terylene twill). The paddedmaterial is squeezed to a liquor uptake of 43 percent referred to thedry weight of the material, and thermofixed for 1 minute at 210 C. Alevel, brilliant red dyeing fast to boiling is obtained.

EXAMPLE ll Dyeing is carried out in the manner described in Example 5,but using the dyestuff of the formula on or We claim:

1. A process for dyeing textile material made from polyamide, polyester,or polyacrylonitrile fibers which consists essentially of applying tosaid textile material a substantially anhydrous solution containing atleast one fiber-reactive dyestuff in a solvent or mixture of solventswhich are substantially inert to the textile material at the temperatureof the application andlwhich is additionally selected from the groupconsisting of cyclohexanol, benzyl alcohol, ethyl acetate, propylacetate, butyl acetate, diisopropylether, diphenyl oxide,methylethylketone, acetophenone, cyclohexanone, benzene, toluene,xylene, carbon tetrachloride, clhloroform, methylene chloride,trichloroethylene, perchloroethylene, tetrachloroethane,dibromoethylene, chlorobenzene, methanol, ethanol, n-propanol,isopropanol, acetone, dioxan, tetrahydrofuran, glycerolformaldehyde,glycolformaldehyde, acetonitrile, pyridine, diacetone alcohol, ethyleneglycol [monoethyllmonomethyl ether, ethylene glycol monoethyl ether,ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, thiodiglycol, ethylene carbonate,y-butyrolactone, N,N-dimethylformamide, N,N- dimethylacetamide,bis-(dimethylamido)-methane phosphate, tris-( dimethylamido )-phosphate,N- methylpyrrolidone, 1,5-dimethylpyrrolidone, N,N-dimethylmethoxy-acetamide, N,N,N,N- tetramethylurea,tetramethylenesulphone, 3-

methylsulpholan and dimethylsolphoxide, drying the textile material, andthereafter heating the textile material to fix the dyestuff thereon byreaction between the fiber-reactive dyestuff and the fibers to form acovalent bond.

2. A process according to claim 1 in which the solvent used is misciblewith water in all proportions.

3. A process according to claim 1 in which the solvent isN,N-dimethylacetamide or N,N-dimethylformamide.

4. A process according to claim 1 in which the solvent used isN-methylpyrrolidone.

5. A process according to claim 1 in which the solvent used istetramethylenesulphone, or 3- methylsulpholan.

6. A process according to claim 1 in which ethylene carbonate orbutyrolactone is the solvent,

7. A process according to claim 1 in which there is incorporated in thedyeing solution a non-ionic surfactant.

8. A process according to claim 1 in which the fiberreactive dyestuffcontains a heterocyclic residue selected from s-triazinyl containing oneor two halogen atoms, said halogen atoms being selected from chlorine orbromine, or pyrimidyl containing one or two chlorine atoms orphenylsulphonyl or methylsulphonyl groups.

9. A process according to claim 1 in which the fiberreactive dyestuffcontains an aliphatic acyl group selected from y-chlorocrotonylamino,a,B-dibromocrotonylamino, B,/3-dibromoacrylamino, a-chloroacrylamino,a,B-bromoacrylamino, monochloroacetyl and monochloroacetylamino.

10. A process according to claim 1 in which the fabric is dried byevaporation prior to fixation of the dyestuff.

2. A process according to claim 1 in which the solvent used is misciblewith water in all proportions.
 3. A process according to claim 1 inwhich the solvent is N,N-dimethylacetamide or N,N-dimethylformamide. 4.A process according to claim 1 in which the solvent used isN-methylpyrrolidone.
 5. A process according to claim 1 in which thesolvent used is tetramethylenesulphone, or 3-methylsulpholan.
 6. Aprocess according to claim 1 in which ethylene carbonate orbutyrolactone is the solvent.
 7. A process according to claim 1 in whichthere is incorporated in the dyeing solution a non-ionic surfactant. 8.A process according to claim 1 in which the fiber-reactive dyestuffcontains a heterocyclic rEsidue selected from s-triazinyl containing oneor two halogen atoms, said halogen atoms being selected from chlorine orbromine, or pyrimidyl containing one or two chlorine atoms orphenylsulphonyl or methylsulphonyl groups.
 9. A process according toclaim 1 in which the fiber-reactive dyestuff contains an aliphatic acylgroup selected from gamma -chlorocrotonylamino, Alpha , Beta-dibromocrotonylamino, Beta , Beta ''-dibromoacrylamino, Alpha-chloroacrylamino, Alpha , Beta -bromoacrylamino, monochloroacetyl andmonochloroacetylamino.
 10. A process according to claim 1 in which thefabric is dried by evaporation prior to fixation of the dyestuff.